CN115322339A - 一种带多支烷氧链的dpp类聚合物及其合成方法与应用 - Google Patents
一种带多支烷氧链的dpp类聚合物及其合成方法与应用 Download PDFInfo
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- CN115322339A CN115322339A CN202210982647.3A CN202210982647A CN115322339A CN 115322339 A CN115322339 A CN 115322339A CN 202210982647 A CN202210982647 A CN 202210982647A CN 115322339 A CN115322339 A CN 115322339A
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- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
本发明公开了一种带多支烷氧链的DPP类聚合物及其合成方法与应用,其结构通式I所示。本发明中,将结构通为式Ⅹ所示的化合物与双甲基锡化合物在配体和催化剂的作用下,在有机溶剂中进行still偶联聚合反应,提纯后得到所述的式I聚合物。带多支烷氧链的DPP类聚合物由于其含有烷氧链,使其在甲醇等溶剂中有很好的溶解性,可以减少在器件制备过程中卤族元素的使用,对人的身体健康以及环境更加友好。本发明的带多支烷氧链的DPP类聚合物为有机半导体层制备的有机场效应晶体管的空穴迁移率最高为0.1cm2V‑1s‑1,在有机场效应晶体管器件中有着良好的应用前景。
Description
技术领域
本发明属于材料领域,具体涉及一种带多支烷氧链的DPP类聚合物及其合成方法与应用。
背景技术
场效应晶体管(field-effect transistors)是通过电场来调控半导体材料导电能力的有源器件,被用来放大和转换电信号。与无机场效应晶体管相比,有机场效应晶体管与之最大的区别就是用有机半导体材料取代了无机半导体材料。有机半导体材料有四大优势:一、可通过简单的化学修饰进行改性;二、具有良好的柔韧性;三、可通过溶液法制备器件;四、低成本。
在有机场效应晶体管中,按照导电沟道中载流子种类,有机半导体材料可以分为p型、n型和双极性,其载流子分别为空穴,电子,空穴和电子。按照材料的分子量来分,可以分为小分子和聚合物材料。聚合物因其较高的黏性和良好的成膜性,被认为是半导体溶液处理方法的一种良好材料,最可能实现大面积柔性器件与电路。一般来说,烷基链在共轭材料中扮演的角色是提高相应材料在有机溶液中的溶解度。除此之外,研究表明烷基链的类别、长度和分叉点的位置对分子堆积、薄膜形态和器件性能也有重要影响,相对于直链烷基链,带多支烷基链的共轭聚合物普遍具有更好的溶解度,同时能极大的改善器件性能。另外,以氧元素取代碳元素的直链烷基链被应用到有机共轭材料中,所得到的聚合物显示出良好溶解度,高分子量以及优异的器件效果。
发明内容
发明目的:本发明的目的是提供一种带多支烷氧链的DPP类聚合物及其合成方法与应用。
技术方案:本发明提供的一种带多支烷氧链的DPP类聚合物,其结构通式如式Ⅰ所示:
所述的式I中Ar为芳香族基团;n为自然数。
所述的式I中Ar基团从下面的基团中选取任意一种:
所述Ar基团中,n为10-150,优选地,n为15或20。
按照本发明的另一方面,提供了一种带多支烷氧链的DPP类聚合物的制备方法,将结构通为式Ⅹ所示的化合物与双甲基锡化合物在配体和催化剂的作用下,在有机溶剂中进行still偶联聚合反应,提纯后得到所述的式I聚合物;
所述的带多支烷氧链的DPP类聚合物的制备方法中,双甲基锡化合物选自如下化合物中的任意一种:
(即5,5’-双(三甲基锡)-2,2’-联二噻吩)、
所述的配体选自三(邻甲苯基)膦、三苯基膦、和三苯基胂中的至少一种。
所述的催化剂选自二(三苯基膦)二氯化钯、四(三苯基膦)钯和三(二亚苄基丙酮)二钯中的至少一种。
所述的式I的制备过程中,式X所示化合物与双甲基锡化合物以及配体和催化剂在氩气的氛围下,在溶剂中加热搅拌反应通过still偶联反应得到式I。
所述的式X所示化合物的投料摩尔份数为1.00份;
所述的双甲基锡化合物的投料摩尔份数为0.80~1.20份;
所述的配体的投料摩尔份数为0.03~0.95份,优选为0.03~0.90份;
所述催化剂的投料摩尔份数为0.01~0.20份,优选为0.01~0.10份;
优选地,所述式X所示化合物、双甲基锡化合物、配体和催化剂的投料摩尔用量比具体为1.0:1.0:0.08:0.02。
优选地,所述的偶联聚合反应温度为90~140℃,具体为130℃。
优选地,所述聚合时间为2小时~80小时,具体时间为72小时。
优选地,所述聚合反应的溶剂具体选自甲苯、氯苯和二甲苯中的一种。
在所述聚合反应完毕后,将所得反应体系冷却后缓慢滴加到正己烷中后过滤,将所得沉淀用索氏提取器依次用甲醇、丙酮、正己烷、乙酸乙酯抽提,抽提至无色后,除去小分子和催化剂,再用三氯甲烷抽提得到式I所述化合物。
按照本发明的另一方面,所述式X所示化合物按照如下步骤制备所得:
步骤(1)化合物Ⅲ的制备:化合物Ⅱ在二氯甲烷做为溶剂的条件下与吡啶和对甲苯磺酰氯进行反应生成化合物Ⅲ
步骤(2)化合物V的制备:化合物Ⅳ在THF作为溶剂的条件下与氢化锂铝在氮气的保护条件下反应生成化合物V:
步骤(3)化合物Ⅵ的制备:化合物Ⅲ和化合物V在THF作为溶剂,氮气的保护条件下,与氢化钠反应生成化合物Ⅵ:
步骤(4)化合物Ⅶ的制备:化合物Ⅵ和三溴化硼-四氢呋喃溶液、氢氧化钠、双氧水在四氢呋喃作为溶剂的条件下反应生成化合物Ⅶ:
步骤(5)化合物Ⅷ的制备:化合物Ⅶ和对甲苯磺酰氯、吡啶在二氯甲烷作为溶剂的条件下反应生成化合物Ⅷ:
步骤(6)化合物Ⅹ的制备:化合物Ⅷ和Ⅸ、碳酸钾、四正丁基溴化铵在DMF作为溶剂的条件下反应生成化合物Ⅹ:
上述方法步骤(1)中,所述化合物Ⅱ和对甲苯磺酰氯以及吡啶的投料比为1:1-2:1-3,优选1:1.2:2,反应步骤中反应温度为0-50℃,反应时间为12-72h。
上述方法步骤(2)中,化合物Ⅳ和氢化锂铝的投料比为1:1.5-2.5,优选1:2.1,反应步骤中反应温度为50-100℃,反应时间为6-18h。
上述方法步骤(3),中化合物V和化合物Ⅲ以及氢化钠的投料比为1:1.5-2.5:2-4,优选1:2:3,反应步骤中反应温度为0-100℃,反应时间为12-36h。
上述方法步骤(4),化合物Ⅵ与三溴化硼-四氢呋喃溶液以及氢氧化钠、双氧水的投料比为1:3-5:3-5:3-5,优选1:4:4:4,反应步骤中反应温度为0-60℃,反应时间为1-5h。
上述方法步骤(5),化合物Ⅶ与对甲苯磺酰氯以及吡啶的投料比为1:1-2:1-3,优选1:1.2:2,反应步骤中反应温度为0-50℃,反应时间为12-72h。
上述方法步骤(6),化合物Ⅸ和化合物Ⅷ与碳酸钾、四正丁基溴化铵的投料比为1:3-5:3-7:0.05-0.2,优选1:4:5:0.1,反应步骤中反应温度为0-150℃,反应时间为12-72h。
上述步骤(1)至步骤(5)所述反应均在有机溶剂中进行。所述步骤(1)和(5)中,所述溶剂具体可为二氯甲烷;所述步骤(2)、(3)和(4)中,所述溶剂具体四氢呋喃;所述步骤(6)中,所述溶剂具体为DMF。
上述本发明所提供的结构通式I所示聚合物在制备OFETs中的应用及含有所提供结构通式I所示聚合物的OFETs,也属于此发明要求保护的范围。所述OFETs,构成半导体层的材料为权利要求1所述结构通式I所示聚合物。
此发明具有以下有益效果有:
(1)原料是已经商业化的产品或有文献报道的产品,合成的路线比较简单,此合成路线也可以借鉴到其他类似物合成的方法中。
(2)带多支烷氧链的DPP类聚合物由于其含有烷氧链,使其在甲醇等溶剂中有很好的溶解性,可以减少在器件制备过程中卤族元素的使用,对人的身体健康以及环境更加友好。
(3)带多支烷氧链的DPP类聚合物有可能应用于有机太阳能电池或者其他的有机光电功能器件中。
(4)以本发明的聚合物作为半导体层制备OFETs的迁移率(μ),PBMDPP-co-TT为单极性有机场效应晶体管,其空穴迁移率最高可达0.1cm2V-1s-1。
附图说明
图1为本发明中的式Ⅹ所示化合物的合成路线;
图2为本发明中的PBMDPP-co-TT聚合物在溶液以及薄膜状态下的紫外可见吸收光谱图;
图3为本发明中的PBMDPP-co-TT的循环伏安曲线图;
图4为本发明中的带多支烷氧链的DPP类聚合物场效应晶体管的结构示意图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。此外,下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
具体实施例1
式I所述化合物的合成路线如图1所示,核磁表征通过仪器Mercury-VX300n(400MHz);质谱表征通过仪器Ion Spec 4.7T FTMS。
1.式Ⅹ所述化合物的制备过程如下:
(1)式Ⅲ所述化合物的制备:式Ⅲ所述化合物的制备:在500ml的圆底烧瓶中依次加入55g(0.7mol)吡啶,42g(0.35mol)化合物Ⅱ和250mL二氯甲烷。在冰浴的条件下,分批将100g(0.5mol)对甲苯磺酰氯加入到反应瓶中,随后在常温下反应40h。后应结束后,用二氯甲烷进行萃取,收集有机相,用无水硫酸钠进行干燥,过滤,旋干。用乙酸乙酯和石油醚(1:1)作为洗脱剂进行柱层析,最终得到65.1g液体Ⅲ。产率为93%
(2)式V所述化合物的制备:在500ml的圆底烧瓶加入250mL无水THF,然后加入50g50g(0.29mol)化合物Ⅳ。在冰浴的条件下,将23.15g(0.61mol)四氢铝锂的THF溶液逐滴加入到500ml的圆底烧瓶中,后在75℃条件下回流反应10h。随后,在冰浴的条件下逐滴加入氢氧化钠溶液,直到无气泡产生,后用二氯甲烷萃取,用乙酸乙酯和石油醚(1:1)作为洗脱剂进行柱层析。最后得到20g化合物V,产率59.3%
(3)式Ⅵ所述化合物的制备:在氩气氛围中,将10.33g(0.26mol)的氢化钠(60%含量)和100mL无水THF加入500mL的圆底烧瓶中,冰浴进行搅拌。然后,将含10g(0.09mmol)化合物V的50mL THF溶液缓慢滴加到上述溶液中(20min)。继续反应一段时间后,将含48g(0.18mol)化合物Ⅲ的160mL THF溶液逐滴加入到反应瓶中,约1h滴加完毕。升温至75℃反应,继续反应24h。随后,过滤,旋干,用乙酸乙酯和石油醚(2:1)作为洗脱剂进行柱层析,得到5.6g黄色油状物Ⅵ,理论产量为12.9g,产率:87%。
(4)式Ⅶ所述化合物的制备:在100mL干燥Schlenk管中(无水无氧)加入5g(12.8mmol)化合物Ⅵ的20mL THF溶液(无水无氧)。在冰浴的条件下,把4.8mL(51mmol)三溴化硼-四氢呋喃溶液逐滴加入到反应瓶中。约20min后滴加完毕,然后在室温的条件下反应1h后,把4.8mL(3M,51mmol)NaOH溶液与10mL水依次滴入反应瓶中,然后在40℃的条件下反应1h,反应完成后冷却至室温。把4.8mL(51mmol)H2O2缓慢加入到反应瓶中。继续在室温的条件下进行反应,约1h后,反应完毕。用1M HCl溶液调节PH至中性,用乙酸乙酯萃取,萃取后用无水硫酸镁进行干燥,过滤旋蒸,得淡黄色液体。用乙酸乙酯和石油醚(2:1)作为洗脱剂进行柱层析,得到8.9g淡黄色产物Ⅶ,理论产量为9.3g,产率:96%
式Ⅶ所述化合物结构表征数据如下:1H NMR(400MHz,CHCl3,δppm)δ3.64-3.55(m,12H),3.38(s,3H),2.39(br,1H);13C NMR(100MHz,CHCl3,δppm)δ72.04,71.92,70.48,70.44,70.41,62.66,58.96,38.66,30.05,24.82;ESI-MS m/z calcd for C16H34O7 338.44[M],found 361.22[(M+23)+]。
(5)式Ⅷ所述化合物的制备:在500mL圆底烧瓶中依次加入9.48g(0.12mol)吡啶、20.03g(0.06mol)化合物Ⅶ和100mL二氯甲烷。在冰浴条件下,分批将17g(0.09mol)对甲苯磺酰氯加入到反应瓶中,并在常温下反应40h,结束反应。后用二氯甲烷进行萃取,收集有机相,用无水硫酸钠进行干燥,过滤,旋干。用乙酸乙酯和石油醚(1:1)作为洗脱剂进行柱层析,最终得到23.24g液体Ⅷ。产率为82%
式Ⅷ所述化合物结构表征数据如下:1H NMR(400MHz,CHCl3,δppm)δ7.79-7.77(d,J=8.16Hz,2H),7.35-7.33(d,J=7.84Hz,2H),4.06-3.93(m,2H),3.64-3.52(m,20H),3.38(s,6H),2.45(s,3H);13C NMR(100MHz,CHCl3,δppm)δ129.89,129.82,127.97,127.89,72.12,71.95,71.81,70.51,70.45,59.03,38.63,30.29,26.31,21.64;ESI-MS m/z calcdfor C23H40O9S 492.62[M],found 493.24[(M+1)+]。
(6)式Ⅹ所述化合物的制备:在100mL圆底烧瓶中,加入0.5g(1.09mmol)化合物Ⅸ,2.05g(4.15mmol)化合物Ⅷ,0.75g(5.45mmol)无水碳酸钾,35.18mg(0.11mmol)四正丁基溴化铵和30mL DMF,在氩气保护下,110℃反应20h,冷却至室温,旋干,然后用氯仿进行萃取,接下来用无水硫酸钠干燥,过滤,旋干的粗产物。用四氢呋喃和石油醚(1:5)作为洗脱剂进行柱层析,得到214.1mg红色固体Ⅹ,产率:17.84%。
式Ⅹ所述化合物结构表征数据如下:1H NMR(400MHz,CHCl3,δppm)δ8.65-8.64(d,J=4.2Hz,2H),7.25-7.24(d,J=4.2Hz,2H),3.98-3.94(t,J=7.8Hz,4H),3.64-3.51(m,36H),3.47-3.38(m,12H),3.36(s,12H);13C NMR(100MHz,CHCl3,δppm)δ160.94,138.90,135.29,131.72,131.08,119.18,107.78,71.96,71.67,70.52,59.03,42.41,38.80,29.69,27.52,25.83;ESI-MS m/z calcd for C46H70Br2N2O14S2 1098.99[M],found 1099.26[(M+1)+]。
2.式XXIⅠ的聚合物PBMDPP-co-TT制备过程如下:
原料为Ⅸ(74.1mg,0.067mmol),Ⅹ(31.40mg)和双组份催化剂Pd2(dba)3(1.23mg,2%)和p(t-ol)3(1.64mg,8%)加入到50ml的Schlenk管中,抽气、充气依次进行三次,加入8mL超干氯苯(除氧),130℃下反应72h后停止反应,反应液缓慢滴入100mL正己烷中,过滤,粗产品先用正己烷,甲醇,丙酮和乙酸乙酯抽提,最后用氯仿抽提,抽提下来的溶液,沉降,真空干燥,得到黑色固体PBMDPP-co-TT。
从以上表征数据可知,该化合物结构为式XXII所示化合物PBMDPP-co-TT结构式如下所示:
本发明的聚合物PBMDPP-co-TT的光谱性能、电化学性能以及场效应晶体管性能如下:
图2为聚合物PBMDPP-co-TT在溶液中和薄膜中的紫外可见吸收光谱。
由图2可知,聚合物PBMDPP-co-TT薄膜的光学带隙分别为1.33eV(光学带隙计算公式Eg=1240/λ,其中Eg为光学带隙,λ为紫外吸收曲线的边界值)。
图3为聚合物PBMDPP-co-TT薄膜的CV曲线。测定在CHI 760E电化学工作站中进行,采用传统的三电极结构测试,玻碳电极为工作电极,铂丝为辅助电极,银/氯化银为参比电极,四丁基六氟磷酸铵作为电解质。测试在乙腈溶液体系中进行。循环伏安的条件为:扫描范围为-2-2伏特(vs.Ag/AgCl),扫描速率为100V/s。该聚合物具有氧化峰和还原峰,可当作有机半导体材料。根据CV曲线,聚合物PBMDPP-co-TT的HOMO能级分别为–5.31eV,LUMO能级分别为–3.98eV。聚合物具有比较合适的HOMO能级和LUMO能级,聚合物PBMDPP-co-TT具有P型材料。
聚合物PBMDPP-co-TT应用于场效应晶体管。图4为有机场效应晶体管的结构示意图。
本发明给出的合成方法简单、有效,对于合成新的有机场效应晶体管材料有很大的指导意义。
本领域的技术人员容易理解,以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (10)
4.如权利要求3所述的带多支烷氧链的DPP类聚合物的制备方法,其特征在于:所述的提纯是在聚合反应完毕后,将所得反应体系冷却后加入到正己烷溶剂后过滤,将所得沉淀物用索氏提取器依次用甲醇、丙酮、正己烷抽提、乙酸乙酯抽提至无色后,再用三氯甲烷抽提得到式I所述化合物。
5.如权利要求3所述的带多支烷氧链的DPP类聚合物的制备方法,其特征在于:所述的双甲基锡化合物为芳香族化合物;
所述的配体为三(邻甲苯基)膦、三苯基膦和三苯基胂中的至少一种;所述的催化剂为二(三苯基膦)二氯化钯、四(三苯基膦)钯和三(二亚苄基丙酮)二钯中的至少一种;
所述的结构通式Ⅹ所示化合物的投料摩尔份数为1.00份;所述的双甲基锡化合物的投料摩尔份数为0.90~1.10份;所述的配体的投料摩尔份数为0.03~0.95份;所述的催化剂的投料摩尔份数为0.01~0.20份;
所述的偶联聚合反应温度为90~140℃,时间为2小时~80小时,反应的溶剂为甲苯、氯苯或二甲苯中的一种。
6.如权利要求5所述的带多支烷氧链的DPP类聚合物的制备方法,其特征在于:所述的偶联聚合反应的温度为130℃,反应时间为72小时。
7.如权利要求3所述的带多支烷氧链的DPP类聚合物的制备方法,其特征在于:所述的式Ⅹ的制备包括如下步骤:
步骤(1)化合物Ⅲ的制备:化合物Ⅱ在二氯甲烷做为溶剂的条件下与吡啶和对甲苯磺酰氯进行反应生成化合物Ⅲ:
其中,所述的化合物Ⅱ和对甲苯磺酰氯以及吡啶的投料比为1:1-2:1-3,反应步骤中反应温度为0-50℃,反应时间为12-72h;
步骤(2)化合物V的制备:化合物Ⅳ在THF作为溶剂的条件下与氢化锂铝在氮气的保护条件下反应生成化合物V:
其中,化合物Ⅳ和氢化锂铝的投料比为1:1.5-2.5,反应步骤中反应温度为50-100℃,反应时间为6-18h;
步骤(3)化合物Ⅵ的制备:化合物Ⅲ和化合物V在THF作为溶剂,氮气的保护条件下,与氢化钠反应生成化合物Ⅵ:
其中,化合物V和化合物Ⅲ以及氢化钠的投料比为1:1.5-2.5:2-4,反应步骤中反应温度为0-100℃,反应时间为12-36h;
步骤(4)化合物Ⅶ的制备:化合物Ⅵ和三溴化硼-四氢呋喃溶液、氢氧化钠、双氧水在四氢呋喃作为溶剂的条件下反应生成化合物Ⅶ:
其中,化合物Ⅵ与三溴化硼-四氢呋喃溶液以及氢氧化钠、双氧水的投料比为1:3-5:3-5:3-5,反应步骤中反应温度为0-60℃,反应时间为1-5h;
步骤(5)化合物Ⅷ的制备:化合物Ⅶ和对甲苯磺酰氯、吡啶在二氯甲烷作为溶剂的条件下反应生成化合物Ⅷ:
其中,化合物Ⅶ与对甲苯磺酰氯以及吡啶的投料比为1:1-2:1-3,反应步骤中反应温度为0-50℃,反应时间为12-72h;
步骤(6)化合物Ⅹ的制备:化合物Ⅷ和Ⅸ、碳酸钾、四正丁基溴化铵在DMF作为溶剂的条件下反应生成化合物Ⅹ:
其中,化合物Ⅸ和化合物Ⅷ与碳酸钾、四正丁基溴化铵的投料比为1:3-5:3-7:0.05-0.2,反应步骤中反应温度为0-150℃,反应时间为12-72h。
8.如权利要求7所述的带多支烷氧链的DPP类聚合物的制备方法,其特征在于:所述的步骤(1)至步骤(5)所述反应均在有机溶剂中进行;所述的步骤(1)和步骤(5)中,溶剂为二氯甲烷;所述的步骤(2)、步骤(3)和步骤(4)中,溶剂为四氢呋喃;所述的步骤(6)中,溶剂为DMF。
9.一种如权利要求1-2任一项所述的带多支烷氧链的DPP类聚合物在制备有机场效应晶体管中的应用。
10.如权利要求9所述的带多支烷氧链的DPP类聚合物在制备有机场效应晶体管中的应用,其特征在于:所述的带多支烷氧链的DPP类聚合物应用于有机场效应晶体管的半导体层。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102775273A (zh) * | 2012-07-05 | 2012-11-14 | 北京大学 | 一种分叉烷基链及其制备和在有机共轭分子中的应用 |
US20130165655A1 (en) * | 2010-09-10 | 2013-06-27 | Ocean's King Lighting Science & Technology Co., Ltd. | Benzodithiophene organic semiconductive material and its preparation method and use |
CN105968326A (zh) * | 2016-05-18 | 2016-09-28 | 中国科学院化学研究所 | 双吡咯并吡咯二酮聚合物的制备方法与应用 |
CN107118335A (zh) * | 2017-06-05 | 2017-09-01 | 华中科技大学 | 异靛青‑双键‑异靛青类聚合物及其合成方法与应用 |
CN114573428A (zh) * | 2020-12-02 | 2022-06-03 | 北京大学 | 含有支化醚链的有机共轭分子及其制备和应用 |
-
2022
- 2022-08-16 CN CN202210982647.3A patent/CN115322339A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130165655A1 (en) * | 2010-09-10 | 2013-06-27 | Ocean's King Lighting Science & Technology Co., Ltd. | Benzodithiophene organic semiconductive material and its preparation method and use |
CN102775273A (zh) * | 2012-07-05 | 2012-11-14 | 北京大学 | 一种分叉烷基链及其制备和在有机共轭分子中的应用 |
CN105968326A (zh) * | 2016-05-18 | 2016-09-28 | 中国科学院化学研究所 | 双吡咯并吡咯二酮聚合物的制备方法与应用 |
CN107118335A (zh) * | 2017-06-05 | 2017-09-01 | 华中科技大学 | 异靛青‑双键‑异靛青类聚合物及其合成方法与应用 |
CN114573428A (zh) * | 2020-12-02 | 2022-06-03 | 北京大学 | 含有支化醚链的有机共轭分子及其制备和应用 |
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